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How to prepare buffers
for pH meters
Theory ,procedure and calculations
Abu Alhassan Abd Elshafi
This document had written in order to more understanding to the nature of buffer working and
to preparation in lab certain pH values to give more accurate results required in quality control
.
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pH meter buffers calculations
Introduction:
Buffer solution: is the solution that able to resistance the change of pH upon
addition of small amount of acid or base .and is used in many experiments to
adjust the pH of solution regardless the source of the sample. Since certain pH is
required for many dyes or coloration solution that used in spectrophotometric
experiments to prevent interference as possible.
Weak acid with its salts and also weak bases with its salts generally are usually
used for preparation of buffer solutions.
Theory:
Let solution contain weak acid and its salt like CH3COOH /CH3COONa
CH3COOH CH3COO- + H+
If we add a small amount of strong acid like HCl .the presence of acetate ion in
the solution reduces the ionization of acetic acid according to Le Chatelier law
for equilibrium .as the following :
CH3COO- + H+ CH3COOH
The H+ ion librated from ionization of the strong acid is combined with acetate
ion to form acetic acid but acetic acid is present in the original solution that
reduce the formation of the acid initially .upon addition of the strong acid ,so
this reduces the change of pH
The same thing occurs if we add strong base to the buffer solution . The OH- ion
librated from ionization of the strong base is reacts with acetic acid as the
following:
CH3COOH +OH- CH3COO - + H2O
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But acetate ion initially present in the original solution ,so according to Le
Chatelier law there is a resistance to the formation acetate ion upon addition of
the strong base so this reduces the change of pH.
Calculation of pH of the buffer solutions
Let the ionization of weak acid like acetic acid
CH3COOH CH3COO- + H+
So ka
Where : Ka is ionization constant
By rearrangement the last equation:
[ ]
[H+]=
[ ]
[ ]
Or pH=pKa+ log
[ ]
The last equation called Henderson equation.
Where :
[acid] =concentration of weak acid
[salt] =concentration of salt of the acid .
The last equation will be the base that all our following calculation will built in.
The same buffer solution value can be prepared from more than one source
But there are siutable combinations that are achieve the aim but reduce the
amounts of chemicals used . and the clever chemist that note this.
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other impotrant note in preparing the buffer solutions:
restore in your mind the Henderson equation
pH= pka+log ([salt]/[acid])
the value ([acid]/[base]) is the variable section in the equation by variaing in
either of acid or salt concentration the pH will be changed but
if this section equals : log([a]/[[b]) ………..(1)
..the same pH value will be if the section equals
Log([m* a]/[m*b] …………(2)
Where m is real numer multiplying in a and b .
What is mean?
Is this means that first choice or possability of preparing the buffer is preffered
since this reduces the use of chemicals?
The answer of this question depends on: what are the uses of the buffer ? what
are the chemicals will be added to it ? etc
In general the use of the second choice is that when we need to increesing the
stability of the buffer value .on other words if we need to add a portion of the
buffer to other solution matrix …and so on ( in the following examples this point
will be explained ).
The purpose and Aim:
Most pH meters needs certain pH points to calibrated ,usually pH=4 ,pH = 7 , pH
= 10 .
Our aim is to prepare the buffer solution that equal to this pH points in lab for
more quality results far from uncertainty.
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The combination of pH meter Elctrode
Most modern electrodes are combined electrodes in which
the Reference and measuring electrodes are coupled
pH is negative logarithm of Hydrogen ion concentration
i.e pH= -log[H+]
By measuring the potential difference between the
potenetionals of reference and measuring electrodes
the concentration of Hydrogen can calculated easily from Nernst Equation
.
E=E0 - log [ ]
where:
E = total potential (in mill volts) between two electrodes
E0 = standard potential of the ion
R = universal gas constant (in Joules/mol-Kelvin)
T = absolute temperature (in Kelvin)
n = charge of the ion
F = Faraday constant (in Coulombs/mol)
The entire term "2.3RT/nF" is called the Nernst factor, or slope factor. This term
provides the amount of change in total potential for every ten-fold change in ion
concentration.
For hydrogen ion activity, where n = 1, the Nernst factor is 59.16 mV for every
ten-fold change in activity at 25°C. This means that for every pH unit change, the
total potential will change 59.16 mV.
The following general equation may be stated for any temperature (since pH is
defined as the negative logarithm of the hydrogen ion activity):
E = E0 + (1.98 x 10-4) TK pH
However, the Nernst factor will change when temperature changes (T is not
constant). At 25°C the slope of the pH electrode is 59.16 mV/pH unit. At 0°C the
slope value is approximately 54 mV/pH, and at 100°C the slope value is
approximately 74 mV/pH.
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The mill volt output of the glass pH electrode will change with temperature in
accordance with the Nernst equation. As the temperature increases, so does the
mill volt output. Specifically, the slope of the electrode
is what changes
The pH measurement is comprised of two half-cell, or electrode, potentials. One
half-cell is the pH sensitive glass measuring electrode and the other is the
reference electrode. Just as the two half-cell potentials of a battery are required
to complete a circuit so does a pH sensor.
The mathematical expression for this is:
E = Em - Er
where:
Em = the electrode potential of the measuring electrode Er= the electrode
potential of the reference electrode This type of measurement, in mill volts, is
referred to as a potentiometric measurement.
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Procedure:
First : preparation of 3 M KCl saturated with AgCl
This solution is used as half cell solution of pH meter Electrode
× . ×
Wt =
Mol.Wt of KCl = 74.6 g /mol
3 × 74.6 × 250
= = 55.95
1000
Dissolve 55.95 g of KCl in distillated water and dilute to 250 ml in measuring flask.
Add about 10 g AgCl to the KCl solution and shake well.
………………………………………………………………………………
………………………………………………………………………………
If there is no packed AgCl we can prepare it in the laboratory as the following:
Mol.Wt of AgNO3 =169.87, Mol.Wt of KCl =74.6 g/mol, AgCl =143.86 g/mol
AgNO3 + KCl KNO3 + AgCl
169.86 74.6 143.86
X y 10
Y =5.19 g of KCl ,,,,, X = 11.81 g of AgNO3
Dissolve AgNO3 and KCl in appropriate volume of distillated water and mix the
two solutions, a Wight PPT will be formed .
filter and wash the PPT more than time until the TDS of filtrate be as least as
possible .
finally add the pure AgCl PPT to 3 M KCl solution . and this solution regards as
KCl solution saturated with AgCl .
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Preparation of pH =4 buffer solution.
Before speaking on the preparation, you must consider the following table:
Series acid Ka pk a base Kb pKb
1 CH 3COOH 1.75X10-5 4.757 NH 4OH 1.71x10-5 4.77
2 benzoic acid 6.28 x 10-5 4.202 Ca(OH)2
3 Boric acid 5.81x10 -10 9.236 8.94
4 formic acid 1.77x10-4 3.75
Phosphoric 3.38
5 4.17x10-4
acid
We will the mixture CH 3COOH /CH3COONa to prepare pH= 4 solution
Ka =1.75 x 10-5 pKa = 4.76
0.1 N acetic acid
[CH3COOH]=0.1 N V=
× . ×
× × %
According to Henderson equation: . × ×
[ ] V= = 1.431
pH = pKa+ log × . × .
[ ]
[ ]
4= 4.76 + log
.
0.01738 N of sod acetate
[ 3 ] [ 3 ]
log =-0.76 =0.1738 V=
. × ×
= 0.591
. .
[CH3COONa] = 0.1 x0.1738 =0.01738 N
**dilute 1.431 ml of acetic acid to 250 ml using
de-ionized water and dissolve 0.591 of sod.acetate
to 250 ml distillated water .
Mix acurate equal volumes of the two solution to prepare pH=4
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Preparation of pH =10 buffer solution.
By the same way we can calculate pH =10 0.1N NH 4OH
× . ×
Using NH4OH /NH4Cl solution V= × × %
Using henderson Equation in the case of bases V
. × ×
= 3.01 =
× . × .
[ ]
pH=pKw-pKb-
[ ]
pKb for NH4Cl = 4.77
0.017 N of NH 4Cl
. × . ×
[ ] V= = 0.2274
10 = 14- 4.77 -log [ . ]
[ ]
log- =9.23 -10=-0.77
[ . ]
[ ]
- =0.17 [NH4Cl]= 0.017 N
.
dilute 3.01 ml of ammonia solution to 250 ml using de-ionized water and
dissolve 0.2274 g of dried ammonium chlorid to 250 ml distillated water .
Mix acurate equal volumes of the two solution to prepare pH=10
Important note :
Many commerial chemicals suppliers don’t give certain value of concentration
but it gaven as range like ammonai (30-33%) for example .
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So for standarized chemical analysis we jast identfy a certain percent concentration of
ammonai solution as the following :
1) Transefer known volume of ammonia stock (V1)
2) Titrate with HCl or H 2SO4 using PhPh. indicator
3) So (N ×V)ammona =(N × V)acid
4) St = Namm × Eq.Wt = A g/L.
5) C% = A/10 = a % W/V ammoania
6) C% = a/ d = a` % V/V ammonia
Where d is the density of ammonai which easly identefied by wieghting a known
volume of ammonia .
Prepration of pH=7 buffer solution .
Phosphate combinations the most chemicals used in preparation of pH range (6-8) .
So we will use the phosphate compounds for this porpose .
Henderson eqaution :
[ ]
pH = pKa+ log
[ ]
the combination Na2HPO4/KH 2PO4 will be used as salt and acid .
i.e Na2HPO4 is regards as the salt , KH2PO4 is regards as the acid .
but before starting the calcultions we must focuse the sight on the following equation
of phosphoric acid and it`s salts dissoctions .
H 3PO 4 ƒ H + +H 2 PO -4 pK a1 = 7.11×10−3
H 2 PO -4 ƒ H + +HPO-24 pK a 2 = 6.32 × 10−8
HPO -24 ƒ H + +PO -34 pK a 3 = 4.5 ×10−13
The phosphoric acid reacts with bases in three stage so the reaction of each stage not
started until the the stage before it was finished.
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The equations above describes the fact that the three reactions occur in three
different pH values approximatly 4.7 , 9.6 ,and 12.3 therefore each reaction end
point needs a siutable indicator for example methyl orange for 1st reaction ,
phph. For 2nd reaction etc .
there is no available indictor in many labs suitable for 3rd reaction so by
stiochiometry we can determine the concentration of phosphoric acid deponding
on 1st or 2nd reaction end points .
pH1= ½(pKa1+pKa2)
pH2= ½(pKa2+pKa3)
using M.O indicator is preferable if H3PO4% >95% but phph or any other indicator
work in the range of second end point is better because sensetivity reasons .
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Determination of phosphoric acid concentration %.
There are more than one method but the famous two methods:
a) Direct titration with strong base Using 1st or 2nd end points
1) take x mL of the acid in flask and dilute it with suitable amount of D.w
2) put a few drops if the indicator
3) titrate with “ a “ N NaOH
4) (N × V)NaOH=(N × V)1st eq pt
5) N phosphoric = N 1st eq pt ×3 in the case of M.O end point
or ( N 2nd eq pt /2) ×3 in the case of PhPh end point
6) C = Nphosphoric × eq .wt = b g/L
7) C% = b /10 = p w/v
8) C%= p/d = e v/v since d is density of phosphric acid .
Example :
1) Weighting 20 mL of Conc. H3PO4 =34.2 g ….So d = 1.71 g /cm3.
2) When Titrating 1 mL of conc H3PO4 with 1 N NaOH using PhPh. End point
the volume taken from NaOH = 30 mL
3) (N × V)NaOH=(N × V)2st eq pt (30 × 1)NaOH =( N × 1) 2st eq pt
So N2st eq pt = 30 N
4) Nphosphoric =(30/2)×3 = 45 N
5) C = Nphosphoric × eq .wt = 45 ×98/3=1470 g/L
6) C%= C/10 = 1470/10 = 147 % w/w
7) C%= 147/1.71 = 86 % v/v (approximatily)
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b) Reaction with CaCl2 and titration the librated HCl .
2H3PO4 + 3 CaCl2 = 2 Ca3(PO4)2 + 6 HCl
1 mole H3PO4 ≈ 3 mole HCl ≈ 3 mole NaOH
1) Take 1 ml of conc. Phosphoric acid . dilute with D.W .
2) Add excess amount of CaCl2. Solution 10 ml 20% CaCl2
3) Add few drops of PhPh. Indicator
4) Titrate with NaOH 1 N
5) (N × V )NaOH =( N × V)phosphoric
6) C= Nphosph × Eq .Wt
7) C% = C/10 w/v%
8) C% = C/(10× 1.71) v/v %
Example:
Standardization of NNaOH= 0.89 N .
Adding excess amount of CaCL2 to approperate amount of D.W
containing of 0.4 mL of H3PO4 and when titrating the amount of NaOH
taken = 20.3 mL
(N ×V)NaOH = (N × V).
20.3 ×0.89 = Nphosphoric × 0.4
Nphosphoric =45.16 N
C (strength) = Nphosphoric × Eq.W = 45.16 × (98/3) =1475.23 g/L
C % = 1475.23 / 10 = 147.523 % wt/v .
C% = 147.523 /1.71 =86.2 % v/v .
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Preparation of pH = 7 buffer solution .
Using Na2HPO4 as salt , KH 2PO 4 as acid ……the dissociation equation of the acid
described as :.
H2PO4- ƒ H+ + HPO4-2
Henderson Equation : 0.1 M KH2PO4 anhydrous.
× . ×
pH = pKa+ log
[ ] Wt =
[ ]
. × . ×
Wt= = 3.4025 g
substituting pKa = 6.865 ,pH= 7 ,[KH 2PO4] = 0.1 M
-------------------------------------------
[salt ]
7 = 6.865 + log 0.1365 M of Na 2HPO4 anhydrous
0.1
. × ×
V= = 4.846
[salt ] [salt ]
0.135= log =100.135 =1.365
0.1 0.1
[salt] = 0.1 × 1.365=0.1365 M
Dissolve 3.4025 g of anhydrous KH2PO4 in approperate amount of distillated water and
complete to 250 mL
Also dissolve 4.846 g of anhydrous Na 2HPO4 in D. W and complete to 250 mL
Mix equal volumes of the two solution to get pH = 7
Now let us to enjoy with advanced calculations in prepration of phosphate buffers
In the following pages .
Lets go ….
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If there is no packed phosphate chemicals present in your lab i.e there is no
either packed Na2HPO4 Nor KH2 PO4 or present but not pure …..etc .
Our aim to prepare these compounds from the orginal source of it !
i.e phosphoric acid (H3PO4) and alkali bases sodium hydroxide (NaOH) and
pottasium hydroxide (KOH).
Preparation of 250 mL 0.1365 M of Na2HPO4 from NaOH and H3PO4
1) Determine the Concentration% of H3PO4 as above
2) Determine the concentration % of NaOH by standarization with either
pottasium hydrogen phthalete or HCl as the following :
Weight 1 g of NaOH and dissolve in 100 mL
Titrate 10 mL of the last solution against 0.25 M HCL
(M × V )MaOH =( M × V)HCl
MNaOH=( 0.25 × V)HCl /10 = 0.025 VHCl
C (strength) = MNaOH × Mol .Wt = 0.025 VHCl × 40 =1 VHCl
C% = Strength /10 = 0.1 VHCl %w/v ( grams NaOH /100 mL Water)
P% NaOH=(C% ×100) /1 %w/w (grams NaOH/100 g NaOH).
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3) From above we calculate the weight must dissolved from Na2HPO4
to prepare 0.1365 and it equal 3.4025 g
so the stoichiometric equations to calculate the amount needed from H 3PO4
and NaOH described as .
2 NaOH + H 3PO4 Na2HPO4 + 2 H 2O
2 mole + 1 mole 1 mole
2× 40 =80 g 98 g 142 g
x y 4.846 g
x= 4.846 × 80 / 142 = 2.73 g (if NaOH % =100 pure ). And x = 2.73 ×100/p% if
NaOH not 100% pure.
y = 4.846 ×98/142 = 3.344 g H 3PO4
or y =( 3.344×100)/(p%× d). mL H 3PO4
if d (density of H 3PO4) = 1.71 g/cm3 , p% =85 .
y = (3.344× 100)/(1.71×85) =2.3 mL H 3PO4 85%
dissolve 2.73 g of NaOH in appropriate amount( about 50 mL) of distillated water and let
it to cold
dilute 2.3 mL of H 3PO4 85% in appropriate amount( about 50 mL) of distillated water
and let it to cold . mix the two solution and complete to 250 mL . with distillated water .
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Preparation of 250 mL 0.1 M of KH2PO4 from KOH and H3PO4
1) Determine the Concentration% of H 3PO 4 as above
2) Determine the concentration P% of KOH by standarization with either
pottasium hydrogen phthalete or HCl as above
3) From above we calculate the weight must dissolved from Na 2HPO4
to prepare 0.1365 and it equal 3.4025 g
so the stoichiometric equations to calculate the amount needed from H 3PO4
and KOH described as .
KOH + H 3PO 4 KH 2PO 4 + H 2O
mole + 1 mole 1 mole
56.1 g 98 g 136.1 g
x y 3.4025 g
x= 3.4025 × 56.1 / 136.1 = 1.4025 g (if KOH % =100 pure ). And x = 1.4025
×100/p% if KOH not 100% pure.
y = 3.4025 ×98/136.1 = 2.45 g H 3PO4
or y =( 2.348×100)/(p%× d). mL H 3PO4
if d (density of H 3PO4) = 1.71 g/cm3 , p% =85 .
y = (2.45× 100)/(1.71×85) =1.69 mL H 3PO4 85%
dissolve 1.4025 g of KOH in appropriate amount( about 50 mL) of distillated water and
let it to cold
dilute 1.69 mL of H 3PO4 85% in appropriate amount( about 50 mL) of distillated water
and let it to cold . mix the two solution and complete to 250 mL . with distillated water
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now to prepare the buffer ph = 7 mix equal volumes from Na2HPO4 and KH2PO4
solutions .
important Notes :
1) You can mix the the calculated amounts of Na2HPO4 and KH2PO4 each in
apprpraite amount of water ( 100 ml) and complete the whole solution to 250
mL ,this give the same result .
2) In page 4 remind the mean of buffer capacity .
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